US20220025168A1 - Thermoplastic Resin Composition and Molded Article Formed Therefrom - Google Patents
Thermoplastic Resin Composition and Molded Article Formed Therefrom Download PDFInfo
- Publication number
- US20220025168A1 US20220025168A1 US17/296,660 US201917296660A US2022025168A1 US 20220025168 A1 US20220025168 A1 US 20220025168A1 US 201917296660 A US201917296660 A US 201917296660A US 2022025168 A1 US2022025168 A1 US 2022025168A1
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- United States
- Prior art keywords
- resin composition
- thermoplastic resin
- weight
- aromatic vinyl
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011342 resin composition Substances 0.000 title claims abstract description 73
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 71
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 19
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims description 57
- 239000011347 resin Substances 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 55
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 44
- -1 poly(ether ester amide Chemical class 0.000 claims description 38
- 229920006164 aromatic vinyl copolymer Polymers 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 229920001400 block copolymer Polymers 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 20
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000005060 rubber Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000002834 transmittance Methods 0.000 claims description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 150000003951 lactams Chemical class 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229920006026 co-polymeric resin Polymers 0.000 abstract description 3
- 230000003068 static effect Effects 0.000 abstract description 3
- 239000004925 Acrylic resin Substances 0.000 abstract 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 21
- 230000006866 deterioration Effects 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000002216 antistatic agent Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 229920012128 methyl methacrylate acrylonitrile butadiene styrene Polymers 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920006352 transparent thermoplastic Polymers 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- BZDKYAZTCWRUDZ-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC=C.C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 BZDKYAZTCWRUDZ-UHFFFAOYSA-N 0.000 description 3
- 229920003244 diene elastomer Polymers 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 2
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 2
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 2
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 2
- RLFXJQPKMZNLMP-UHFFFAOYSA-N 2-phenylprop-2-enenitrile Chemical compound N#CC(=C)C1=CC=CC=C1 RLFXJQPKMZNLMP-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 239000004429 Calibre Substances 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920006033 core shell type graft co-polymer Polymers 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DEAKWVKQKRNPHF-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 DEAKWVKQKRNPHF-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/04—Polyadducts obtained by the diene synthesis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Definitions
- the present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. More particularly, the present invention relates to a thermoplastic resin composition that exhibits good properties in terms of antistatic properties, transparency, impact resistance, and the like, and a molded article manufactured therefrom.
- a reinforced glass product used as external materials for electric/electronic products has low impact strength, a high specific gravity causing difficulty in weight reduction of products, high manufacturing costs due to difficulty in processing and handling, and a risk of fracture.
- a transparent resin replaces such a reinforced glass product.
- Transparent resins applicable to products requiring transparency comprise a polycarbonate resin, a transparent ABS resin, a SAN resin, a polystyrene resin, a PMMA resin, and the like.
- a product formed of a typical transparent thermoplastic resin composition exhibits very low absorptivity with respect to moisture in air and accumulates static electricity therein without discharging the static electricity causing surface contamination, electrostatic impact, malfunction, or failure of devices through adsorption of dust in air.
- a typical antistatic agent can be used to secure antistatic properties of the transparent thermoplastic resin composition and products (molded articles) formed therefrom, an excess of the antistatic agent is used to achieve suitable antistatic properties, causing deterioration in compatibility, mechanical properties, chemical resistance, transparency, and the like of the thermoplastic resin composition.
- thermoplastic resin composition that exhibits good properties in terms of antistatic properties, transparency, impact resistance, and the like.
- the background technique of the present invention is disclosed in Korean Patent Laid-open Publication No. 2007-0108008 and the like.
- thermoplastic resin composition that exhibits good properties in terms of antistatic properties, transparency, impact resistance, and the like.
- thermoplastic resin composition comprises: about 100 parts by weight of a rubber-modified aromatic vinyl copolymer resin comprising a rubber-modified vinyl graft copolymer and an aromatic vinyl copolymer resin; about 0.1 to about 15 parts by weight of a poly(alkyl (meth)acrylate) resin; about 5 to about 20 parts by weight of a poly(ether ester amide) block copolymer; and about 0.2 to about 5 parts by weight of sodium perchlorate (NaClO 4 ).
- the rubber-modified aromatic vinyl copolymer resin may comprise about 5 wt % to about 50 wt % of the rubber-modified vinyl graft copolymer and about 50 wt % to about 95 wt % of the aromatic vinyl copolymer resin.
- the poly(ether ester amide) block copolymer and the sodium perchlorate may be present in a weight ratio of about 15:1 to about 25:1.
- the rubber-modified vinyl graft copolymer may be obtained through graft copolymerization of an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer to a rubber polymer.
- the aromatic vinyl copolymer resin may be obtained through copolymerization of an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer.
- the poly(ether ester amide) block copolymer may be a block copolymer of a reaction mixture comprising a salt of an amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms.
- the poly(alkyl (meth)acrylate) resin may have a weight average molecular weight of about 50,000 g/mol to about 130,000 g/mol and a glass transition temperature of about 90° C. to about 110° C.
- thermoplastic resin composition may have a surface resistance of about 1 ⁇ 10 7 to about 5 ⁇ 10 10 ⁇ /sq, as measured in accordance with ASTM D257.
- thermoplastic resin composition may have a haze value of about 2% to about 6% and a light transmittance of about 87% to about 96%, as measured on a 2.5 mm thick specimen in accordance with ASTM D1003.
- thermoplastic resin composition may have a notched Izod impact strength of about 12 kgf ⁇ cm/cm to about 20 kgf ⁇ cm/cm, as measured on a 1 ⁇ 8′′ thick specimen in accordance with ASTM D256.
- Another aspect of the present invention relates to a molded article formed of the thermoplastic resin composition according to any one of Embodiments 1 to 10.
- the present invention provides a thermoplastic resin composition that has good properties in terms of antistatic properties, transparency, impact resistance, and the like, and a molded article formed of the same.
- thermoplastic resin composition according to the present invention comprises: (A) a rubber-modified aromatic vinyl copolymer resin; (B) a poly(alkyl (meth)acrylate) resin; (C) a poly(ether ester amide) block copolymer; and (D) sodium perchlorate (NaClO 4 ).
- the rubber-modified aromatic vinyl copolymer resin according to the present invention may be selected from any rubber-modified aromatic vinyl copolymer resins used in a typical transparent thermoplastic resin composition and may comprise, for example, (A1) a rubber-modified vinyl graft copolymer and (A2) an aromatic vinyl copolymer resin.
- the rubber-modified vinyl graft copolymer according to the present invention serves to improve transparency, impact resistance, and flowability of the thermoplastic resin composition, and may be obtained through graft-copolymerization of an alkyl (meth)acrylate, an aromatic vinyl monomer and a vinyl cyanide monomer to a rubber polymer.
- the rubber-modified vinyl graft copolymer may be obtained through graft-copolymerization of a monomer mixture comprising the alkyl (meth)acrylate, the aromatic vinyl monomer and the vinyl cyanide monomer to the rubber polymer and, optionally, the monomer mixture may further comprise a monomer for imparting processability and heat resistance.
- the polymerization may be performed by any suitable polymerization method known in the art, such as emulsion polymerization, suspension polymerization, and mass polymerization.
- the rubber polymer may comprise diene rubbers, such as polybutadiene, poly(styrene-butadiene), and poly(acrylonitrile-butadiene), saturated rubbers obtained by adding hydrogen to the diene rubbers, isoprene rubbers, acrylic rubbers, such as poly(butyl acrylate), and ethylene-propylene-diene terpolymer (EPDM). These may be used alone or as a mixture thereof.
- the rubber polymer may comprise diene rubbers, specifically a butadiene rubber.
- the rubber polymer (rubber particles) may have an average (z-average) particle diameter of about 0.1 ⁇ m to about 0.5 ⁇ m, for example, about 0.2 ⁇ m to about 0.4 ⁇ m.
- the thermoplastic resin composition can have good properties in terms of impact resistance, heat resistance, flowability, and the like without deterioration in transparency.
- the average (Z-average) particle diameter of the rubber polymer (rubber particles) may be measured by a light scattering method in a latex state. Specifically, a rubber polymer latex is filtered through a mesh to remove coagulum generated during polymerization of the rubber polymer.
- a mixed solution of 0.5 g of the latex and 30 ml of distilled water is placed in a 1,000 ml flask, which in turn is filled with distilled water to prepare a specimen. Then, 10 ml of the specimen is transferred to a quartz cell, followed by measurement of the average particle diameter of the rubber polymer using a light scattering particle analyzer (Malvern Co., Ltd., Nano-zs).
- the rubber polymer may be present in an amount of about 5 wt % to about 65 wt %, for example, about 10 wt % to about 60 wt %, based on the total weight (100 wt %) of the rubber-modified vinyl graft copolymer, and the monomer mixture (comprising the alkyl (meth)acrylate, the aromatic vinyl monomer and the vinyl cyanide monomer) may be present in an amount of about 35 wt % to about 95 wt %, for example, about 40 wt % to about 90 wt %, based on 100 wt % of the rubber-modified vinyl graft copolymer.
- the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- the alkyl (meth)acrylate may be graft copolymerizable with the rubber polymer or the aromatic vinyl monomer and may comprise a C 1 to C 10 alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and the like, specifically methyl (meth)acrylate.
- the alkyl (meth)acrylate may be present in an amount of about 55 wt % to about 85 wt %, for example, about 60 wt % to about 80 wt %, based on 100 wt % of the monomer mixture.
- the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- the aromatic vinyl monomer may be graft copolymerizable with the rubber polymer and may comprise, for example, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, and the like. These may be used alone or as a mixture thereof.
- the aromatic vinyl monomer may be present in an amount of about 10 wt % to about 40 wt %, for example, about 15 wt % to about 35 wt %, based on 100 wt % of the monomer mixture.
- the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- the vinyl cyanide monomer is a monomer copolymerizable with the aromatic vinyl monomer and may comprise, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, ⁇ -chloroacrylonitrile, and fumaronitrile, without being limited thereto. These may be used alone or as a mixture thereof.
- the vinyl cyanide monomer may be acrylonitrile, methacrylonitrile, and the like.
- the vinyl cyanide monomer may be present in an amount of about 1 wt % to about 30 wt %, for example, about 5 wt % to about 25 wt %, based on 100 wt % of the monomer mixture.
- the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- the monomer for imparting processability and heat resistance may comprise, for example, (meth)acrylic acid, maleic anhydride, and N-substituted maleimide, without being limited thereto.
- the monomer for imparting processability and heat resistance may be present in an amount of about 15 wt % or less, for example, about 0.1 wt % to about 10 wt %, based on 100 wt % of the monomer mixture. Within this range, the monomer for imparting processability and heat resistance can impart processability and heat resistance to the thermoplastic resin composition without deterioration in other properties.
- the rubber-modified vinyl graft copolymer may be a methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS).
- the g-MABS may comprise polybutadiene (PBD), which constitutes the rubber polymer (core), and a methyl methacrylate-acrylonitrile-styrene copolymer shell grafted to the core, in which the shell may comprise an inner shell comprising an acrylonitrile-styrene resin and an outer shell comprising poly(methyl methacrylate), without being limited thereto.
- PBD polybutadiene
- the shell may comprise an inner shell comprising an acrylonitrile-styrene resin and an outer shell comprising poly(methyl methacrylate), without being limited thereto.
- the rubber-modified vinyl graft copolymer may be present in an amount of about 5 wt % to about 50 wt %, for example, about 10 wt % to about 45 wt %, based on 100 wt % of the rubber-modified aromatic vinyl copolymer resin.
- the thermoplastic resin composition can exhibit good properties in terms of transparency, impact resistance, heat resistance, flowability, and balance therebetween.
- the aromatic vinyl copolymer resin according to the present invention serves to improve impact resistance, transparency, and the like of the thermoplastic resin composition, and may be a polymer of a monomer mixture comprising an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer.
- the aromatic vinyl copolymer resin may be obtained through polymerization of the monomer mixture by a polymerization method known in the art.
- the monomer mixture may further comprise a monomer for imparting processability and heat resistance, as needed.
- the alkyl (meth)acrylate may be graft copolymerizable with the rubber copolymer or may be copolymerizable with the aromatic vinyl monomer, and may be a C 1 to C 10 alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and the like, specifically methyl (meth)acrylate.
- the alkyl (meth)acrylate may be present in an amount of about 55 wt % to about 85 wt %, for example, about 60 wt % to about 80 wt %, based on 100 wt % of the monomer mixture.
- the thermoplastic resin composition can exhibit good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- the aromatic vinyl monomer is graft copolymerizable with the rubber copolymer and may comprise, for example, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinyl naphthalene. These may be used alone or as a mixture thereof.
- the aromatic vinyl monomer may be present in an amount of about 10 wt % to about 40 wt %, for example, about 15 wt % to about 35 wt %, based on 100 wt % of the monomer mixture.
- the thermoplastic resin composition can exhibit good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- the vinyl cyanide monomer may be copolymerizable with the aromatic vinyl monomer and may comprise, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, ⁇ -chloroacrylonitrile, and fumaronitrile, without being limited thereto. These may be used alone or as a mixture thereof.
- the vinyl cyanide monomer may comprise acrylonitrile, methacrylonitrile, and the like.
- the vinyl cyanide monomer may be present in an amount of about 1 wt % to about 30 wt %, for example, about 5 wt % to about 25 wt %, based on 100 wt % of the monomer mixture.
- the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- the monomer for imparting processability and heat resistance may comprise, for example, (meth)acrylic acid, maleic anhydride, and N-substituted maleimide, without being limited thereto.
- the monomer for imparting processability and heat resistance may be present in an amount of about 15 wt % or less, for example, about 0.1 wt % to about 10 wt %, based on 100 wt % of the monomer mixture. Within this range, the monomer for imparting processability and heat resistance can impart processability and heat resistance to the thermoplastic resin composition without deterioration in other properties.
- the aromatic vinyl copolymer resin may have a weight average molecular weight (Mw) of about 50,000 g/mol to about 200,000 g/mol, for example, about 100,000 g/mol to about 180,000 g/mol, as measured by gel permeation chromatography (GPC). Within this range, the thermoplastic resin exhibits good heat resistance, processability, and the like.
- Mw weight average molecular weight
- the aromatic vinyl copolymer resin may be present in an amount of about 50 wt % to about 95 wt %, for example, about 55 wt % to about 90 wt %, based on 100 wt % of a base resin.
- the thermoplastic resin composition can exhibit good properties in terms of transparency, impact resistance, heat resistance, flowability, balance therebetween, and the like.
- the base resin (rubber-modified aromatic vinyl copolymer resin) may be, for example, a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (MABS resin), which is a mixture of a methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS) and a methyl methacrylate-styrene-acrylonitrile copolymer resin (MSAN), without being limited thereto.
- the MABS resin may have a structure in which g-MABS is dispersed in MSAN.
- the poly(alkyl (meth)acrylate) resin according to the present invention serves to improve compatibility, transparency, antistatic properties, impact resistance, and the like of the thermoplastic resin composition together with the poly(ether ester amide) block copolymer.
- the poly(alkyl (meth)acrylate) resin may be a polymer of a monomer comprising at least one C 1 to C 10 alkyl (meth)acrylate obtained by a polymerization method well-known in the art, for example, poly(methyl (meth)acrylate) (PMMA), poly(ethyl (meth)acrylate), poly(propyl (meth)acrylate), methyl (meth)acrylate, and a copolymer of a C 2 to C 10 alkyl (meth)acrylate, specifically poly(methyl methacrylate).
- the poly(alkyl (meth)acrylate) resin may be a transparent thermoplastic resin having a weight average molecular weight of about 50,000 g/mol to about 130,000 g/mol, for example, about 60,000 g/mol to about 120,000 g/mol, as measured by GPC (gel permeation chromatography). Within this range, the thermoplastic resin composition can have good transparency, impact resistance, and the like.
- the poly(alkyl (meth)acrylate) resin may have a glass transition temperature of about 90° C. to about 110° C., for example, about 95° C. to about 110° C. Within this range, the thermoplastic resin composition can have good heat resistance, compatibility, and the like.
- the poly(alkyl (meth)acrylate) resin may be present in an amount of about 0.1 to about 15 parts by weight, for example, about 1 to about 10 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the poly(alkyl (meth)acrylate) resin is less than about 0.1 parts by weight, the thermoplastic resin composition can suffer from deterioration in compatibility, antistatic properties, impact resistance, and the like, and if the content of the poly(alkyl (meth)acrylate) resin exceeds about 15 parts by weight, the thermoplastic resin composition can suffer from deterioration in antistatic properties, transparency, and the like.
- the poly(ether ester amide) block copolymer according to the present invention serves to improve antistatic properties of the thermoplastic resin composition (specimen) and may be selected from among typical poly(ether ester amide) block copolymers used as an antistatic agent, for example, a block copolymer of a reaction mixture comprising a salt of an amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms.
- typical poly(ether ester amide) block copolymers used as an antistatic agent for example, a block copolymer of a reaction mixture comprising a salt of an amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms.
- the salt of the amino carboxylic acid, lactam, or diamine-dicarboxylate having 6 or more carbon atoms may comprise aminocarboxylic acids, such as ⁇ -aminocaproic acid, ⁇ -aminoenanthic acid, ⁇ -aminocaprylic acid, ⁇ -aminopelargonic acid, ⁇ -aminocapric acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, and the like; lactams, such as caprolactam, enantolactam, laurolactam, and the like; and salts of diamines and dicarboxylic acids, such as salts of hexamethylenediamine-adipic acid, salts of hexamethylenediamine-isophthalic acid, and the like.
- aminocarboxylic acids such as ⁇ -aminocaproic acid, ⁇ -aminoenanthic acid, ⁇ -aminocaprylic acid
- the polyalkylene glycol may comprise polyethylene glycol, poly(1,2- and 1,3-propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, a block or random copolymer of ethylene glycol and propylene glycol, and a copolymer of ethylene glycol and tetrahydrofuran.
- polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, and the like may be used.
- the C 4 to C 20 dicarboxylic acid may comprise terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid, and dodecane carboxylic acid.
- a bond between the salt of the amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms and the polyalkylene glycol may be an ester bond; a bond between the salt of the amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms and the C 4 to C 20 dicarboxylic acid may be an amide bond; and a bond between the polyalkylene glycol and the C 4 to C 20 dicarboxylic acid may be an ester bond.
- the poly(ether ester amide) block copolymer may be prepared by a method well-known in the art, for example, by a method disclosed in JP Patent Publication No. S56-045419 or JP Unexamined Patent Publication No. S55-133424.
- the poly(ether ester amide) block copolymer may comprise about 10 wt % to about 95 wt % of the polyether-ester block.
- the thermoplastic resin composition can have good antistatic properties, heat resistance, and the like.
- the poly(ether ester amide) block copolymer may be present in an amount of about 5 to about 20 parts by weight, for example, about 7 to about 15 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the poly(ether ester amide) block copolymer is less than about 5 parts by weight, the thermoplastic resin composition can suffer from deterioration in antistatic properties, and if the content of the poly(ether ester amide) block copolymer exceeds about 20 parts by weight, the thermoplastic resin composition can suffer from deterioration in impact resistance, transparency, and the like.
- sodium perchlorate serves to improve antistatic properties, impact resistance and the like of the thermoplastic resin composition together with the poly(ether ester amide) block copolymer.
- the sodium perchlorate may be present in an amount of about 0.2 to about 5 parts by weight, for example, about 0.3 to about 5 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the sodium perchlorate is less than about 0.2 parts by weight, the thermoplastic resin composition can suffer from deterioration in transparency, antistatic properties, chemical resistance, and the like, and if the content of the sodium perchlorate exceeds about 5 parts by weight, the thermoplastic resin composition can suffer from deterioration in impact resistance, transparency, and the like.
- the poly(ether ester amide) block copolymer and the sodium perchlorate may be present in a weight ratio of about 15:1 to about 25:1, for example, about 16:1 to about 23:1. Within this range, the thermoplastic resin composition can exhibit good properties in terms of antistatic properties, transparency (transmittance, haze), and the like.
- the thermoplastic resin composition may further comprise additives, such as flame retardants, fillers, an antioxidant agent, a lubricant, a release agent, a nucleating agent, a stabilizer, a colorant, and a mixture thereof, without being limited thereto.
- additives may be present in an amount of about 10 parts by weight or less, for example, about 0.01 to about 10 parts by weight, relative to about 100 parts by weight of the base resin (the rubber-modified aromatic vinyl copolymer resin), without being limited thereto.
- the thermoplastic resin composition may be prepared in pellet form by mixing the aforementioned components, followed by melt extrusion using a typical twin-screw extruder at about 200° C. to about 280° C., for example, about 210° C. to about 250° C.
- the thermoplastic resin composition may have a surface resistance of about 1 ⁇ 10 7 ⁇ /sq to about 5 ⁇ 10 10 ⁇ /sq, for example, about 1 ⁇ 10 7 ⁇ /sq to about 2 ⁇ 10 10 ⁇ /sq, as measured on a specimen having a size of 10 mm ⁇ 10 mm ⁇ 3.2 mm in accordance with ASTM D257.
- the thermoplastic resin composition may have a haze value of about 2% to about 6%, for example, about 2% to about 5.5%, and a light transmittance of about 87% to about 96%%, for example, about 88% to about 96%, as measured on a 2.5 mm thick specimen in accordance with ASTM D1003.
- the thermoplastic resin composition may have an Izod impact strength of about 12 kgf ⁇ cm/cm to about 20 kgf ⁇ cm/cm, for example, about 13 kgf ⁇ cm/cm to about 20 kgf ⁇ cm/cm, as measured on a 1 ⁇ 8′′ thick specimen in accordance with ASTM D256.
- a molded article according to the present invention is produced from the thermoplastic resin composition.
- the thermoplastic resin composition may be prepared in pellet form and the prepared pellets may be produced into various molded articles (products) by various molding methods, such as injection molding, extrusion, vacuum molding, casting, and the like. Such molding methods are well known to those skilled in the art.
- the molded articles exhibit good properties in terms of antistatic properties, transparency, impact resistance, and balance therebetween, and thus may be used in various fields comprising interior/exterior materials for electric/electronic products, and the like.
- the molded article is useful as materials for semiconductor trays and the like.
- g-MABS core-shell type graft copolymer obtained through graft copolymerization of 45 wt % of styrene, acrylonitrile and methyl methacrylate (styrene/acrylonitrile/methyl methacrylate: 20 wt %/10 wt %/70 wt %) to 55 wt % of butadiene rubber particles having an average particle diameter of 0.28 m was used.
- Poly(methyl methacrylate) resin (PMMA, weight average molecular weight: 70,000 g/mol, glass transition temperature: 106° C.) was used.
- the prepared pellets were dried at 80° C. for 4 hours or more and injection-molded in a 6 oz. injection molding machine (molding temperature: 230° C., mold temperature: 60° C.), thereby preparing specimens.
- the prepared specimens were evaluated as to the following properties by the following method, and results are shown in Table 1.
- Haze and transmittance (unit: %): Haze and transmittance were measured on a 2.5 mm thick specimen using a haze meter NDH 2000 (Nippon Denshoku Co., Ltd.) in accordance with ASTM D1003.
- Notched Izod impact resistance (kgf ⁇ cm/cm): Notched Izod impact strength was measured on a 1 ⁇ 8′′ thick specimen in accordance with ASTM D256.
- thermoplastic resin compositions (Examples 1 to 3) according to the present invention exhibited good properties in terms of antistatic properties, impact resistance, transparency, and balance therebetween.
- thermoplastic resin composition of Comparative Example 1 prepared using the olefin antistatic agent (C2) instead of the poly(ether ester amide) block copolymer suffered from deterioration in impact resistance, transparency, and the like
- thermoplastic resin composition of Comparative Examples 2 and 3 prepared using LiClO 4 (D2) and NaBF 4 (D3) instead of sodium perchlorate (NaClO 4 ) suffered from deterioration in transparency (transmittance, haze) and the like.
- thermoplastic resin composition (Comparative Example 4) prepared using a small amount of the poly(ether ester amide) block copolymer and an excess of sodium perchlorate suffered from deterioration in impact resistance, transparency, and the like
- thermoplastic resin composition (Comparative Example 5) prepared using an excess of the poly(ether ester amide) block copolymer and a small amount of sodium perchlorate suffered from deterioration in transparency (transmittance, haze) and the like.
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Abstract
Description
- The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. More particularly, the present invention relates to a thermoplastic resin composition that exhibits good properties in terms of antistatic properties, transparency, impact resistance, and the like, and a molded article manufactured therefrom.
- A reinforced glass product used as external materials for electric/electronic products has low impact strength, a high specific gravity causing difficulty in weight reduction of products, high manufacturing costs due to difficulty in processing and handling, and a risk of fracture. In order to overcome such drawbacks, a transparent resin replaces such a reinforced glass product. Transparent resins applicable to products requiring transparency comprise a polycarbonate resin, a transparent ABS resin, a SAN resin, a polystyrene resin, a PMMA resin, and the like.
- However, a product formed of a typical transparent thermoplastic resin composition exhibits very low absorptivity with respect to moisture in air and accumulates static electricity therein without discharging the static electricity causing surface contamination, electrostatic impact, malfunction, or failure of devices through adsorption of dust in air. Although a typical antistatic agent can be used to secure antistatic properties of the transparent thermoplastic resin composition and products (molded articles) formed therefrom, an excess of the antistatic agent is used to achieve suitable antistatic properties, causing deterioration in compatibility, mechanical properties, chemical resistance, transparency, and the like of the thermoplastic resin composition.
- Therefore, there is a need for development of a thermoplastic resin composition that exhibits good properties in terms of antistatic properties, transparency, impact resistance, and the like.
- The background technique of the present invention is disclosed in Korean Patent Laid-open Publication No. 2007-0108008 and the like.
- It is one object of the present invention to provide a thermoplastic resin composition that exhibits good properties in terms of antistatic properties, transparency, impact resistance, and the like.
- It is another object of the present invention to provide a molded article formed of the thermoplastic resin composition.
- The above and other objects of the present invention can be achieved by the present invention described below.
- 1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises: about 100 parts by weight of a rubber-modified aromatic vinyl copolymer resin comprising a rubber-modified vinyl graft copolymer and an aromatic vinyl copolymer resin; about 0.1 to about 15 parts by weight of a poly(alkyl (meth)acrylate) resin; about 5 to about 20 parts by weight of a poly(ether ester amide) block copolymer; and about 0.2 to about 5 parts by weight of sodium perchlorate (NaClO4).
- 2. In Embodiment 1, the rubber-modified aromatic vinyl copolymer resin may comprise about 5 wt % to about 50 wt % of the rubber-modified vinyl graft copolymer and about 50 wt % to about 95 wt % of the aromatic vinyl copolymer resin.
- 3. In Embodiment 1 or 2, the poly(ether ester amide) block copolymer and the sodium perchlorate may be present in a weight ratio of about 15:1 to about 25:1.
- 4. In Embodiments 1 to 3, the rubber-modified vinyl graft copolymer may be obtained through graft copolymerization of an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer to a rubber polymer.
- 5. In Embodiments 1 to 4, the aromatic vinyl copolymer resin may be obtained through copolymerization of an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer.
- 6. In Embodiments 1 to 5, the poly(ether ester amide) block copolymer may be a block copolymer of a reaction mixture comprising a salt of an amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms.
- 7. In Embodiments 1 to 6, the poly(alkyl (meth)acrylate) resin may have a weight average molecular weight of about 50,000 g/mol to about 130,000 g/mol and a glass transition temperature of about 90° C. to about 110° C.
- 8. In Embodiments 1 to 7, the thermoplastic resin composition may have a surface resistance of about 1×107 to about 5×1010 Ω/sq, as measured in accordance with ASTM D257.
- 9. In Embodiments 1 to 8, the thermoplastic resin composition may have a haze value of about 2% to about 6% and a light transmittance of about 87% to about 96%, as measured on a 2.5 mm thick specimen in accordance with ASTM D1003.
- 10. In Embodiments 1 to 8, the thermoplastic resin composition may have a notched Izod impact strength of about 12 kgf·cm/cm to about 20 kgf·cm/cm, as measured on a ⅛″ thick specimen in accordance with ASTM D256.
- 11. Another aspect of the present invention relates to a molded article formed of the thermoplastic resin composition according to any one of Embodiments 1 to 10.
- The present invention provides a thermoplastic resin composition that has good properties in terms of antistatic properties, transparency, impact resistance, and the like, and a molded article formed of the same.
- Hereinafter, embodiments of the present invention will be described in detail.
- A thermoplastic resin composition according to the present invention comprises: (A) a rubber-modified aromatic vinyl copolymer resin; (B) a poly(alkyl (meth)acrylate) resin; (C) a poly(ether ester amide) block copolymer; and (D) sodium perchlorate (NaClO4).
- As used herein to represent a specific numerical range, the expression “a to b” means “≥a and ≤b”.
- (A) Rubber-Modified Aromatic Vinyl Copolymer Resin
- The rubber-modified aromatic vinyl copolymer resin according to the present invention may be selected from any rubber-modified aromatic vinyl copolymer resins used in a typical transparent thermoplastic resin composition and may comprise, for example, (A1) a rubber-modified vinyl graft copolymer and (A2) an aromatic vinyl copolymer resin.
- (A1) Rubber-Modified Vinyl Graft Copolymer
- The rubber-modified vinyl graft copolymer according to the present invention serves to improve transparency, impact resistance, and flowability of the thermoplastic resin composition, and may be obtained through graft-copolymerization of an alkyl (meth)acrylate, an aromatic vinyl monomer and a vinyl cyanide monomer to a rubber polymer. For example, the rubber-modified vinyl graft copolymer may be obtained through graft-copolymerization of a monomer mixture comprising the alkyl (meth)acrylate, the aromatic vinyl monomer and the vinyl cyanide monomer to the rubber polymer and, optionally, the monomer mixture may further comprise a monomer for imparting processability and heat resistance. Here, the polymerization may be performed by any suitable polymerization method known in the art, such as emulsion polymerization, suspension polymerization, and mass polymerization.
- In some embodiments, the rubber polymer may comprise diene rubbers, such as polybutadiene, poly(styrene-butadiene), and poly(acrylonitrile-butadiene), saturated rubbers obtained by adding hydrogen to the diene rubbers, isoprene rubbers, acrylic rubbers, such as poly(butyl acrylate), and ethylene-propylene-diene terpolymer (EPDM). These may be used alone or as a mixture thereof. For example, the rubber polymer may comprise diene rubbers, specifically a butadiene rubber.
- In some embodiments, the rubber polymer (rubber particles) may have an average (z-average) particle diameter of about 0.1 μm to about 0.5 μm, for example, about 0.2 μm to about 0.4 μm. Within this range, the thermoplastic resin composition can have good properties in terms of impact resistance, heat resistance, flowability, and the like without deterioration in transparency. Here, the average (Z-average) particle diameter of the rubber polymer (rubber particles) may be measured by a light scattering method in a latex state. Specifically, a rubber polymer latex is filtered through a mesh to remove coagulum generated during polymerization of the rubber polymer. Then, a mixed solution of 0.5 g of the latex and 30 ml of distilled water is placed in a 1,000 ml flask, which in turn is filled with distilled water to prepare a specimen. Then, 10 ml of the specimen is transferred to a quartz cell, followed by measurement of the average particle diameter of the rubber polymer using a light scattering particle analyzer (Malvern Co., Ltd., Nano-zs).
- In some embodiments, the rubber polymer may be present in an amount of about 5 wt % to about 65 wt %, for example, about 10 wt % to about 60 wt %, based on the total weight (100 wt %) of the rubber-modified vinyl graft copolymer, and the monomer mixture (comprising the alkyl (meth)acrylate, the aromatic vinyl monomer and the vinyl cyanide monomer) may be present in an amount of about 35 wt % to about 95 wt %, for example, about 40 wt % to about 90 wt %, based on 100 wt % of the rubber-modified vinyl graft copolymer. Within this range, the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- In some embodiments, the alkyl (meth)acrylate may be graft copolymerizable with the rubber polymer or the aromatic vinyl monomer and may comprise a C1 to C10 alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and the like, specifically methyl (meth)acrylate. The alkyl (meth)acrylate may be present in an amount of about 55 wt % to about 85 wt %, for example, about 60 wt % to about 80 wt %, based on 100 wt % of the monomer mixture. Within this range, the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- In some embodiments, the aromatic vinyl monomer may be graft copolymerizable with the rubber polymer and may comprise, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, and the like. These may be used alone or as a mixture thereof. The aromatic vinyl monomer may be present in an amount of about 10 wt % to about 40 wt %, for example, about 15 wt % to about 35 wt %, based on 100 wt % of the monomer mixture. Within this range, the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- In some embodiments, the vinyl cyanide monomer is a monomer copolymerizable with the aromatic vinyl monomer and may comprise, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, α-chloroacrylonitrile, and fumaronitrile, without being limited thereto. These may be used alone or as a mixture thereof. For example, the vinyl cyanide monomer may be acrylonitrile, methacrylonitrile, and the like. The vinyl cyanide monomer may be present in an amount of about 1 wt % to about 30 wt %, for example, about 5 wt % to about 25 wt %, based on 100 wt % of the monomer mixture. Within this range, the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- In some embodiments, the monomer for imparting processability and heat resistance may comprise, for example, (meth)acrylic acid, maleic anhydride, and N-substituted maleimide, without being limited thereto. The monomer for imparting processability and heat resistance may be present in an amount of about 15 wt % or less, for example, about 0.1 wt % to about 10 wt %, based on 100 wt % of the monomer mixture. Within this range, the monomer for imparting processability and heat resistance can impart processability and heat resistance to the thermoplastic resin composition without deterioration in other properties.
- In some embodiments, the rubber-modified vinyl graft copolymer may be a methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS). Here, the g-MABS may comprise polybutadiene (PBD), which constitutes the rubber polymer (core), and a methyl methacrylate-acrylonitrile-styrene copolymer shell grafted to the core, in which the shell may comprise an inner shell comprising an acrylonitrile-styrene resin and an outer shell comprising poly(methyl methacrylate), without being limited thereto.
- In some embodiments, the rubber-modified vinyl graft copolymer may be present in an amount of about 5 wt % to about 50 wt %, for example, about 10 wt % to about 45 wt %, based on 100 wt % of the rubber-modified aromatic vinyl copolymer resin. Within this range, the thermoplastic resin composition can exhibit good properties in terms of transparency, impact resistance, heat resistance, flowability, and balance therebetween.
- (A2) Aromatic Vinyl Copolymer Resin
- The aromatic vinyl copolymer resin according to the present invention serves to improve impact resistance, transparency, and the like of the thermoplastic resin composition, and may be a polymer of a monomer mixture comprising an alkyl (meth)acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer. For example, the aromatic vinyl copolymer resin may be obtained through polymerization of the monomer mixture by a polymerization method known in the art. Further, the monomer mixture may further comprise a monomer for imparting processability and heat resistance, as needed.
- In some embodiments, the alkyl (meth)acrylate may be graft copolymerizable with the rubber copolymer or may be copolymerizable with the aromatic vinyl monomer, and may be a C1 to C10 alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and the like, specifically methyl (meth)acrylate. The alkyl (meth)acrylate may be present in an amount of about 55 wt % to about 85 wt %, for example, about 60 wt % to about 80 wt %, based on 100 wt % of the monomer mixture. Within this range, the thermoplastic resin composition can exhibit good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- In some embodiments, the aromatic vinyl monomer is graft copolymerizable with the rubber copolymer and may comprise, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinyl naphthalene. These may be used alone or as a mixture thereof. The aromatic vinyl monomer may be present in an amount of about 10 wt % to about 40 wt %, for example, about 15 wt % to about 35 wt %, based on 100 wt % of the monomer mixture. Within this range, the thermoplastic resin composition can exhibit good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- In some embodiments, the vinyl cyanide monomer may be copolymerizable with the aromatic vinyl monomer and may comprise, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, α-chloroacrylonitrile, and fumaronitrile, without being limited thereto. These may be used alone or as a mixture thereof. For example, the vinyl cyanide monomer may comprise acrylonitrile, methacrylonitrile, and the like. The vinyl cyanide monomer may be present in an amount of about 1 wt % to about 30 wt %, for example, about 5 wt % to about 25 wt %, based on 100 wt % of the monomer mixture. Within this range, the thermoplastic resin composition can have good properties in terms of impact resistance, transparency, heat resistance, flowability, and the like.
- In some embodiments, the monomer for imparting processability and heat resistance may comprise, for example, (meth)acrylic acid, maleic anhydride, and N-substituted maleimide, without being limited thereto. The monomer for imparting processability and heat resistance may be present in an amount of about 15 wt % or less, for example, about 0.1 wt % to about 10 wt %, based on 100 wt % of the monomer mixture. Within this range, the monomer for imparting processability and heat resistance can impart processability and heat resistance to the thermoplastic resin composition without deterioration in other properties.
- In some embodiments, the aromatic vinyl copolymer resin may have a weight average molecular weight (Mw) of about 50,000 g/mol to about 200,000 g/mol, for example, about 100,000 g/mol to about 180,000 g/mol, as measured by gel permeation chromatography (GPC). Within this range, the thermoplastic resin exhibits good heat resistance, processability, and the like.
- In some embodiments, the aromatic vinyl copolymer resin may be present in an amount of about 50 wt % to about 95 wt %, for example, about 55 wt % to about 90 wt %, based on 100 wt % of a base resin. Within this range, the thermoplastic resin composition can exhibit good properties in terms of transparency, impact resistance, heat resistance, flowability, balance therebetween, and the like.
- In some embodiments, the base resin (rubber-modified aromatic vinyl copolymer resin) may be, for example, a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (MABS resin), which is a mixture of a methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS) and a methyl methacrylate-styrene-acrylonitrile copolymer resin (MSAN), without being limited thereto. Here, the MABS resin may have a structure in which g-MABS is dispersed in MSAN.
- (B) Poly(Alkyl (Meth)Acrylate) Resin
- The poly(alkyl (meth)acrylate) resin according to the present invention serves to improve compatibility, transparency, antistatic properties, impact resistance, and the like of the thermoplastic resin composition together with the poly(ether ester amide) block copolymer.
- In some embodiments, the poly(alkyl (meth)acrylate) resin may be a polymer of a monomer comprising at least one C1 to C10 alkyl (meth)acrylate obtained by a polymerization method well-known in the art, for example, poly(methyl (meth)acrylate) (PMMA), poly(ethyl (meth)acrylate), poly(propyl (meth)acrylate), methyl (meth)acrylate, and a copolymer of a C2 to C10 alkyl (meth)acrylate, specifically poly(methyl methacrylate).
- In some embodiments, the poly(alkyl (meth)acrylate) resin may be a transparent thermoplastic resin having a weight average molecular weight of about 50,000 g/mol to about 130,000 g/mol, for example, about 60,000 g/mol to about 120,000 g/mol, as measured by GPC (gel permeation chromatography). Within this range, the thermoplastic resin composition can have good transparency, impact resistance, and the like.
- In some embodiments, the poly(alkyl (meth)acrylate) resin may have a glass transition temperature of about 90° C. to about 110° C., for example, about 95° C. to about 110° C. Within this range, the thermoplastic resin composition can have good heat resistance, compatibility, and the like.
- In some embodiments, the poly(alkyl (meth)acrylate) resin may be present in an amount of about 0.1 to about 15 parts by weight, for example, about 1 to about 10 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the poly(alkyl (meth)acrylate) resin is less than about 0.1 parts by weight, the thermoplastic resin composition can suffer from deterioration in compatibility, antistatic properties, impact resistance, and the like, and if the content of the poly(alkyl (meth)acrylate) resin exceeds about 15 parts by weight, the thermoplastic resin composition can suffer from deterioration in antistatic properties, transparency, and the like.
- (C) Poly(Ether Ester Amide) Block Copolymer
- The poly(ether ester amide) block copolymer according to the present invention serves to improve antistatic properties of the thermoplastic resin composition (specimen) and may be selected from among typical poly(ether ester amide) block copolymers used as an antistatic agent, for example, a block copolymer of a reaction mixture comprising a salt of an amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms; polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms.
- In some embodiments, the salt of the amino carboxylic acid, lactam, or diamine-dicarboxylate having 6 or more carbon atoms may comprise aminocarboxylic acids, such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, and the like; lactams, such as caprolactam, enantolactam, laurolactam, and the like; and salts of diamines and dicarboxylic acids, such as salts of hexamethylenediamine-adipic acid, salts of hexamethylenediamine-isophthalic acid, and the like. For example, 1,2-aminododecanoic acid, caprolactam, and salts of hexamethylenediamine-adipic acid may be used.
- In some embodiments, the polyalkylene glycol may comprise polyethylene glycol, poly(1,2- and 1,3-propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, a block or random copolymer of ethylene glycol and propylene glycol, and a copolymer of ethylene glycol and tetrahydrofuran. For example, polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, and the like may be used.
- In some embodiments, the C4 to C20 dicarboxylic acid may comprise terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid, and dodecane carboxylic acid.
- In some embodiments, a bond between the salt of the amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms and the polyalkylene glycol may be an ester bond; a bond between the salt of the amino carboxylic acid, lactam or diamine-dicarboxylic acid having 6 or more carbon atoms and the C4 to C20 dicarboxylic acid may be an amide bond; and a bond between the polyalkylene glycol and the C4 to C20 dicarboxylic acid may be an ester bond.
- In some embodiments, the poly(ether ester amide) block copolymer may be prepared by a method well-known in the art, for example, by a method disclosed in JP Patent Publication No. S56-045419 or JP Unexamined Patent Publication No. S55-133424.
- In some embodiments, the poly(ether ester amide) block copolymer may comprise about 10 wt % to about 95 wt % of the polyether-ester block. Within this range, the thermoplastic resin composition can have good antistatic properties, heat resistance, and the like.
- In some embodiments, the poly(ether ester amide) block copolymer may be present in an amount of about 5 to about 20 parts by weight, for example, about 7 to about 15 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the poly(ether ester amide) block copolymer is less than about 5 parts by weight, the thermoplastic resin composition can suffer from deterioration in antistatic properties, and if the content of the poly(ether ester amide) block copolymer exceeds about 20 parts by weight, the thermoplastic resin composition can suffer from deterioration in impact resistance, transparency, and the like.
- (D) Sodium Perchlorate
- According to the present invention, sodium perchlorate (NaClO4) serves to improve antistatic properties, impact resistance and the like of the thermoplastic resin composition together with the poly(ether ester amide) block copolymer.
- In some embodiments, the sodium perchlorate may be present in an amount of about 0.2 to about 5 parts by weight, for example, about 0.3 to about 5 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the sodium perchlorate is less than about 0.2 parts by weight, the thermoplastic resin composition can suffer from deterioration in transparency, antistatic properties, chemical resistance, and the like, and if the content of the sodium perchlorate exceeds about 5 parts by weight, the thermoplastic resin composition can suffer from deterioration in impact resistance, transparency, and the like.
- In some embodiments, the poly(ether ester amide) block copolymer and the sodium perchlorate may be present in a weight ratio of about 15:1 to about 25:1, for example, about 16:1 to about 23:1. Within this range, the thermoplastic resin composition can exhibit good properties in terms of antistatic properties, transparency (transmittance, haze), and the like.
- According to one embodiment of the invention, the thermoplastic resin composition may further comprise additives, such as flame retardants, fillers, an antioxidant agent, a lubricant, a release agent, a nucleating agent, a stabilizer, a colorant, and a mixture thereof, without being limited thereto. The additives may be present in an amount of about 10 parts by weight or less, for example, about 0.01 to about 10 parts by weight, relative to about 100 parts by weight of the base resin (the rubber-modified aromatic vinyl copolymer resin), without being limited thereto.
- According to one embodiment of the invention, the thermoplastic resin composition may be prepared in pellet form by mixing the aforementioned components, followed by melt extrusion using a typical twin-screw extruder at about 200° C. to about 280° C., for example, about 210° C. to about 250° C.
- In some embodiments, the thermoplastic resin composition may have a surface resistance of about 1×107 Ω/sq to about 5×1010 Ω/sq, for example, about 1×107 Ω/sq to about 2×1010 Ω/sq, as measured on a specimen having a size of 10 mm×10 mm×3.2 mm in accordance with ASTM D257.
- In some embodiments, the thermoplastic resin composition may have a haze value of about 2% to about 6%, for example, about 2% to about 5.5%, and a light transmittance of about 87% to about 96%%, for example, about 88% to about 96%, as measured on a 2.5 mm thick specimen in accordance with ASTM D1003.
- In some embodiments, the thermoplastic resin composition may have an Izod impact strength of about 12 kgf·cm/cm to about 20 kgf·cm/cm, for example, about 13 kgf·cm/cm to about 20 kgf·cm/cm, as measured on a ⅛″ thick specimen in accordance with ASTM D256.
- A molded article according to the present invention is produced from the thermoplastic resin composition. The thermoplastic resin composition may be prepared in pellet form and the prepared pellets may be produced into various molded articles (products) by various molding methods, such as injection molding, extrusion, vacuum molding, casting, and the like. Such molding methods are well known to those skilled in the art. The molded articles exhibit good properties in terms of antistatic properties, transparency, impact resistance, and balance therebetween, and thus may be used in various fields comprising interior/exterior materials for electric/electronic products, and the like. In particular, the molded article is useful as materials for semiconductor trays and the like.
- Next, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustration only and are not to be construed in any way as limiting the invention.
- Details of components used in Examples and Comparative Examples are as follows.
- (A) Rubber-modified aromatic vinyl copolymer resin
- (A1) Rubber-modified vinyl graft copolymer
- A core-shell type graft copolymer (g-MABS) obtained through graft copolymerization of 45 wt % of styrene, acrylonitrile and methyl methacrylate (styrene/acrylonitrile/methyl methacrylate: 20 wt %/10 wt %/70 wt %) to 55 wt % of butadiene rubber particles having an average particle diameter of 0.28 m was used.
- (A2) Aromatic vinyl copolymer resin
- A resin (weight average molecular weight: 160,000 g/mol) obtained through polymerization of 70 wt % of methyl methacrylate, 20 wt % of styrene and 10 wt % of acrylonitrile was used.
- (B) Poly(alkyl (meth)acrylate) resin
- Poly(methyl methacrylate) resin (PMMA, weight average molecular weight: 70,000 g/mol, glass transition temperature: 106° C.) was used.
- (C) Antistatic agent
- (C1) Poly(ether ester amide) block copolymer (PA6-PEO, Manufacturer: Sanyo, Model: PELECTRON AS) was used.
- (C2) PP-PEO olefin-based antistatic agent (Manufacturer: Sanyo, Model: UC) was used.
- (D1) Sodium perchlorate (NaClO4, Manufacturer: Calibre Chemical) was used.
- (D2) LiClO4 (Manufacturer: Sigma Aldrich, 98%) was used.
- (D3) NaBF4 (Manufacturer: Sigma Aldrich, 98%) was used.
- The above components were mixed in amounts as listed in Table 1 and subjected to melt-extrusion using a twin-screw extruder (L/D=36, (D: Φ45 mm) under conditions of 230° C. and 250 rpm, thereby preparing pellets. The prepared pellets were dried at 80° C. for 4 hours or more and injection-molded in a 6 oz. injection molding machine (molding temperature: 230° C., mold temperature: 60° C.), thereby preparing specimens. The prepared specimens were evaluated as to the following properties by the following method, and results are shown in Table 1.
- Property Measurement
- (1) Surface resistance (unit: Q/sg): Surface resistance was measured on a specimen having a size of 10 mm×10 mm×3.2 mm using a surface resistance tester (Model: Hiresta-UP (MCP-HT450), Manufacturer: Mitsubishi Chemical Co., Ltd.) in accordance with ASTM D257.
- (3) Haze and transmittance (unit: %): Haze and transmittance were measured on a 2.5 mm thick specimen using a haze meter NDH 2000 (Nippon Denshoku Co., Ltd.) in accordance with ASTM D1003.
- (3) Notched Izod impact resistance (kgf·cm/cm): Notched Izod impact strength was measured on a ⅛″ thick specimen in accordance with ASTM D256.
-
TABLE 1 Example Comparative Example 1 2 3 1 2 3 4 5 (A) (wt %) (A1) 30 30 30 30 30 30 30 30 (A2) 70 70 70 70 70 70 70 70 (B) (parts by weight) 5 5 5 5 5 5 5 5 (C) (parts by (C1) 7 10 15 — 10 10 3 21 weight) (C2) — — — 10 — — — — (D) (parts by (D1) 0.4 0.5 0.7 0.5 — — 6 0.1 weight) (D2) — — — — 0.5 — — — (D3) — — — — — 0.5 — — Surface resistance (Ω/sq) 2 × 1010 1 × 109 5 × 108 3 × 1011 8 × 1010 6 × 1010 5 × 1011 2 × 109 Haze (%) 3.2 3.5 5.0 9.0 8.0 8.5 91 6.0 Light transmittance (%) 91 90 88 84 86 85 20 87 Notched Izod impact 15 15 17 11 15 15 8 18 strength (kgf · cm/cm) *parts by weight: parts by weight relative to 100 parts by weight of base resin (A) - From the results, it could be seen that the thermoplastic resin compositions (Examples 1 to 3) according to the present invention exhibited good properties in terms of antistatic properties, impact resistance, transparency, and balance therebetween.
- On the contrary, it could be seen that the thermoplastic resin composition of Comparative Example 1 prepared using the olefin antistatic agent (C2) instead of the poly(ether ester amide) block copolymer suffered from deterioration in impact resistance, transparency, and the like, and the thermoplastic resin composition of Comparative Examples 2 and 3 prepared using LiClO4 (D2) and NaBF4 (D3) instead of sodium perchlorate (NaClO4) suffered from deterioration in transparency (transmittance, haze) and the like. Further, it could be seen that the thermoplastic resin composition (Comparative Example 4) prepared using a small amount of the poly(ether ester amide) block copolymer and an excess of sodium perchlorate suffered from deterioration in impact resistance, transparency, and the like, and the thermoplastic resin composition (Comparative Example 5) prepared using an excess of the poly(ether ester amide) block copolymer and a small amount of sodium perchlorate suffered from deterioration in transparency (transmittance, haze) and the like.
- It should be understood that various modifications, changes, alterations, and equivalent embodiments can be made by those skilled in the art without departing from the spirit and scope of the present invention.
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